Pitchy composition and a method of making it



Patented Dec. 18, 1951 PITCHY COMPOSITION AND A METHOD OF MAKING IT Otto Frans Valdemar Frick, Stockholm, Sweden No Drawing. Application April 29, 1948, Serial No. 24,096. In Sweden March 13, 1948 14 Claims. 1

This invention relates to a method for preparing a material which isinsoluble in water and is resistant against atmospheric agents or the like and more particularly to a method for preparing a material, that is especially suitable for building purposes for instance in floor, wall, ceiling, roof or street coatings but may be used, also for many other purposes, for instance as insulating material, rust preventer or the like, and to the composition of matter so made.

In the method according to the invention a certain pitch is used containing high molecular resinous and fatty acids which is obtained as a bituminous residue by separating for instance by means of steam distillation in vacuo, the resinous andfatty acids boiling at a relatively low temperature from tall oil which is prepared by addition of a mineral acid to the sulphate soap obtained in the alkaline methods of paper pulp making. Said pitchy residue which is a commercial product will not decompose in any essentia1 degree when subjected to heating belowa temperature of about 260 C. W V

. According to the invention the resistant ma .terial is prepared by bringing said pitchy residue in melted or dissolved state to combine one or more metals with exception of the mono-valent alkali metals and intimately mixing the metal salt so produced with a filler in an amount of,

.50 to 95 per cent of weight of the final product.

The pitchy residue which after having been combined with one or several of the metals mentioned above is intended to act as binder may partly be substituted by another binding material suchas natural or synthetic resins, for instance vinyl resins, phenoplasts and/or drying oils and/or resinous acids or saturated or unsaturated fatty acids, especially of the drying type, for instance linseed oil. l

, With reference to the fatty acids the saturated ones are intended to serve as plasticizers whilst the; object. of the unsaturated ones is to give the final-product certain elastic properties.

Sometimes 'it is preferable to replace the pitchy residue with colophony or rosin, for instance of the American, French or Swedish type.

A substitution of part of the pitchy residue with rosin results in an increase of the melting point and the softening point of the final product because rosin has a higher melting point than the pitchy residue. While the melting pointof the residue is about 30 to 45 C. the melting point of rosin is about 125 C. A corresponding difference exists between the softening points of the two substances.

The total amount of the binder shallbe at least 5 to per cent of weight and preferably 15 tog;

20 per cent of weight. or the final product. The metal salts of the pitchy residue may amount to at least 30 and preferably 50 per cent ofweight of the total amount of the binder, i. ve. about 3.3 to 15 per cent of weight of the final product.

If the pitchy residue is partly replaced, by rosin it is preferred to use the rosin in an amountof 3 to 15 per cent of weight and for instancelO per cent of weight of the amount of the pitchy residue.

At the preparation it is generallyto prefer to mixthe pitchy residue or the'rosin with the filler before combining the pitchy residue or therosin with the aforesaid metals. This is especially true when one of the metals is aluminum, because the aluminum soap formed if vprepared in advance can be mixed with. the filler only at a relatively high temperature. The corresponding zinc compound, however, is miscible with the filler even at relatively low temperatures. 7

When the pitchy residue is partly replaced, by rosin or fatty acids it is often suitable to bring also the rosin or the fatty acids into reaction with the metals mentioned above.

When the pitchy residue and the binder-respectively is to be mixed with the filler, the tempera,- ture as mentioned. aboveshall be so high that the pitchy residue and the binder respectivelyexists in melted state. Generally it is to prefer to use a temperature of at least C. During and/or after the addition of the pitchy residue the filler may be stirred very carefully.v for instancein a kneading machine of common types.

As fillers both organicand inorganic substances may be used separately or in admixture. Suitable fillers are: minerals or' rocks in pulverised or fibrous form, for instance asbests,v rock wool, glass wool, fullers earth'quartz sand, pulverised glass or silicon carbide. Asbests may be used in fibrous or ground state. If quartz sand, for instance sea sand is used it may be as fine as possible. I f

The organic fillers may be fibrousand the following may be mentioned: cotton linters, mechanical or chemical paper pulp, rayon fibers, fibrous synthetic resins, for .instancenylon.

Generally, the amount of fibrous fillers used may be varied within a wide range, especially if the tensile strength of the fibers is relatively high. However, if the tensile strength of the fibersis very low, the amountof organic fibrous fillers must not betoo high; this is especially true when tear sustaining slabs for buildingpurposes, for instance fioor slabs should be produced; in this case the. amount of fibrous fillers may not exceed a few per cent of the total amount of fillers. However, if the slabs may have a relativel ow tear strength as in case of wall sheets, the percentage of fibrous fillers may amount to avery high value, for instance 80 per cent of the total product.

As fillers, organic or inorganic dye stuffs may be used also.

As an example of those metals which should be combined with the acids of the pitchy residue or the rosin or other acidous additions the following ones may be mentioned: Cu, Mg, Zn, the metals of the calcium group, for instance calcium, barium, the metals of the iron group, for instance Fe, Al, Cr, Mn.

The metals may preferably be used in form of their oxides, hydroxides or salts, especially very soluble salts.

If these compounds before the addition are dissolved or suspended in water and the binder is not prepared in advance the mixture, consisting of binder and filler, may be heated to a temperature not above but below the boiling point of water at normal pressure or vacuum, whereby explosion like formation of steam is prevented. After the addition of the waterous metal compound the temperature of the mixture should be elevated above the boiling point thus driving off the water.

The temperature must be raised so much that the binder softens or melts again; otherwise a very careful stirring will often not result in an homogeneous mixture between the filler and the metal soap formed.

On the other hand, if the binder is prepared before the addition of the filler it is preferred to remove the total amount of water before the addition of the filler, but then the binder must of course be transformed to a fluid state in any suitable way, before the filler is added. This may be performed by heating the binder until it melts or by the addition of a suitable solvent with adjusted volatility, such as kerosene, turpetine, for instance in an amount of about five per cent of the amount of binder. Said solvent may be removed from the mass and the recovered.

It is suitable to add a solvent to the mass when fibrous fillers, for instance fibrous asbests, are used because an enough high amount of solvent will result in such a soft or highly fluent mixture that the fibrous material will not break at the mixing operation.

Specific examples will now be given of methods of preparing a material for surface coating.

Example 1 A mixture of 30 kilograms of a pitchy residue from the distillation of tall oil produced by AB Bergviks Hartsprodukter, Sweden, and having a melting point of 37 C. and 1.7 kilograms of rosin (from the same firm) was added to another mixture consisting of 9.7 kilograms fibrous asbests of the quality R.'7, 1.5 kilograms cotton linters, kilograms Spanish red and 2.0 kilograms umber. The ingredients were mixed in a kneading machine during which operation the temperature was slowly raised till about 90 C.

'In the meantime 12 kilograms crystallized aluminum sulphate was dissolved in liters water. To the solution so formed 14 kilograms finely ground lime stone, containing about 6.0 kilograms Ca CO3, was added, whereby a mixture of calcium sulphate and aluminum hydroxide is formed and CO2 escapes. When the reaction solution has been allowed to stand a few hours the precipitate consisting of calcium sulphate and aluminum hydroxide and nonreact'ed lime stone may be removed by filtration or decantation.

When the mixture in the kneading machine has been homogeneous and its temperature if it were above C. has decreased till below 100 C., for instance 70 to 80 C. owing to self-cooling the precipitate consisting of calcium sulphate and aluminum hydroxide et cetera is introduced into the kneading machine. The object with cooling the mixture before the precipitate is introduced is as mentioned above to prevent an explosionlike steam formation, when the precipitate is stirred into the mixture. It is not possible to dry the precipitate in advance because then it will loose its property of reacting with weak acids present in pitchy residue from the distillation of tall oil and other starting materials. Thereupon the mixture in the kneading machine is heated till about C. in order to have the pitchy residue to react completely with the precipitate and in order to remove the water accompanying the precipitate or formed in the reaction between the precipitate and the pitchy residue. When the water has been removed the mixture may preferably be stirred, for instance at a temperature of at least C. in order to make it homogeneous.

From the mixture so formed slabs, sheets, plates or boards may be formed, for instance by calendering. At said operation the material may first pass between two rolls or calenders one of which is rotating at a higher speed than the other. The rolls may have a temperature of about 60 C. and may be so spaced that a cylindr-ical layer with a thickness of about 7 centimeters is iormed on the roll rotating at the higher speed. Said roll may have a diameter of about 400 millimeters and from said roll the material is removed when it has been out perpendicularly to the rolling direction, 1. e. parallel to the axis of the rolls. The sheet so formed is then introduced into a calender machine with oiled calenders in which the sheet is rolled in opposite direction to a thickness of about 3 millimeters. The object of oiling the calenders is to prevent the sheet from adhering the rolls. Afterwards the rolled sheet is cut and put into a heating chamber where it is heated till a temperature of about 60 to 90 C. during a time of 12 to 48 hours. Thereby the water will be removed and the mass consolidated. Further the sheets will be shrimp-free. After being dried the sheets are stamped into a suitable size.

The aluminum precipitate used in this example may be substituted by aluminum hydroxide which may be prepared by precipitation from aluminum sulphate by means of ammonia alkali carbonate or caustic alkalies in corresponding amounts. It is also possible to use the precipitate consisting of aluminum hydroxide and barium hydroxide which is obtained at the addition of barium carbonate to a solution of aluminum sulphate.

point of 37 to 38 C 29 Fibrous asbestos 57 Finely grounded asbestos 57 Zinc oxide 3 Lithopon 19 Iron oxide red Quartz sandin when the water has been driven off.

arsvepes Alternatively 3 kilograms of the amount of said pitchy residue maybe replaced by rosin.

The pitchy residue isheated till above its melting point and is mixed with the zinc oxide. If rosin is used together with the pitchy residue, said two substances are mixed before the zinc oxide is added. After the addition of zinc oxide the temperature is raised abve.100 C., whereby steam evolves from the mass i s In the meantim the other ingredients viz. the fibrous and. the finely ground asbestos, the zinc lithopon, the iron oxide red and the quartz sand are intimately mixed and heated till about 100 C. The mixture so formed is then added to the pitchy residue to which previously the zinc oxide and eventually the rosin has been added. When the ingredients have been thoroughly mixed by intimate stirring, the mass is allowed to cooltand is then rolled in the same way as in Example; 1.

.If a fibrousfiller is used and it have a tendencyto break during. the stirring operation, it may be convenient toadd the greatest part .of same at the end of theymixing operation, i. e.

If the mass have to be marbled or veined said appearance may: be obtained in. the. followin of the mass. When the mass-comes into therolling machine, the pieces of the crushed sheets will be stretched in the rolling direction. .The cylindrical layer which adheres to the roll rotating at the highest speed is the cut as mentioned above. The cut-ofi sheet should then'be rolled in a direction perpendicular to the direction of the first rollingin order to make the appearance asestheticas possible,

The sheets or slabs produced according to this invention may be used for instance as floor or wall slabs and may be fastened to the floor or the, wall or to each other by means of a thin layer of asphalt.

It will be understood that various modifications may be made in the specific procedures described 1 without departing from the scope of invention.

What I claim and desire to secure by Letters Patent is:

1. A method of preparing a material for roofing or flooring or insulating purposes or the like comprising combining at a temperature below cracking and above 100 C. a noncracked pitchy residue obtained by vacuum steam distillation of tall oil with a non-dried aluminum hydroxide, precipitated from a soluble aluminum salt, mixing the aluminum metal salt so formed with fibrous and powdered fillers, said aluminum salt and said fillers being employed in a ratio of approximately 50 to 95 per cent by weight of the latter and 5 to 50 per cent by weight of the former.

2. A method of preparing a material for roofing or flooring or insulating purposes or the like comprising mixing a noncracked pitchy residue obtained by vacuum steam distillation of tall oil with rosin, said residue and said rosin being employed in a ratio of approximately 3 to per cent by weight of the latter and 97 to 85 per cent by weight of the former, combining at a temperature below cracking and above 100 C. said noncracked pitchy residue and said rosin with aqueous aluminum hydroxide and mixing the aluminum salts so formed with a filler containing fibrous and powdered substances, said aluminum salts and said filler being employed in a ratio of approximately to per cent by weight of the latter and 15.130 20 per. cent by. weightof the-former.

3. A method of preparing a material for roofing or flOOIiIIg or'insulating; purposes or the like comprising mixing afiller containing fibrous and powdered substances with a melted mixtureof rosin and ainoncracked pitchy residue obtained by-vacuum steam distillation of tall oil, said mixture and saidfiller being employed in a ratio of approximately 80v to 85 per cent by weight of the latter and 15 to 20 per cent byweight of the former, cooling-the mixture till below 100C adding aqueous aluminum hydroxide in an .amountsufficientfor forming aluminum salt of acids of..said pitchy residue and said rosin, heating the mixture till above 100 C. in order to remove the water.

. 4. Composition of matter comprising an-aluminum salt of a noncracked pitchy residue-obtained by vacuum steam distillation of tall oil and. of rosin, said aluminum salt of said residue and said aluminum salt of said rosin being employed in a ratio of 3 to 15 per cent by weight .of the latterand 97 to 85 per cent by weight of the former, anda filler containing powdered and fibrous substances, said aluminum salts and said filler being employed in a ratio of approximately 80 to 85 per cent by weight of the latter and 20 t 15 per cent by weight of the former.

5. Composition of matter comprising a zinc salt of noncracked pitchy residue obtained by vacuum steam distillation of tall oil and filler containing fibrous and powdered substances, said zinc salt and said filler being employed in a ratio of approximately 80 to 85 per cent by weight of the latter and 20 to 15 per cent by weight of the former. i

6. A method of preparing a material for roofing or flooring or insulating purposes or the like, comprising combining at a temperature below cracking and above 100 C. a noncracked pitchy residue obtained by vacuum steam distillation of tall oil with a wet polyvalent metal oxide neutralizer and mixing the metal salt so formed with a filler, said metal salt and said filler being employed in a ratio of approximately 50 to per 'cent by weight of the latter and 5 to 50 per cent by weight of the former.

7. A method of preparing a material for roofing or flooring or insulating purposes or the like, comprising mixing a noncracked pitchy residue obtained by vacuum steam distillation of tall oil with an organic substance containing a fatty acid, combining at a temperature below cracking and above C. said pitchy residue and said organic substance with a wet metal oxide neutralizer of group II of the periodic system and mixing the metal salts so formed with a filler, said metal salts and said filler being employed in a ratio of approximately 50 to 95 per cent by weight of the latter and 5 to 50 per cent by weight of the former.

8. A method of preparing material for roofing or flooring or insulating purposes or the like, comprising mixing a noncracked pitchy residue obtained by vacuum steam distillation of tall oil with rosin, said residue and said rosin being employed in a ratio of approximately 3 to 15 per cent by weight of the latter and 97 to 85 per cent by weight of the former, combining at a temperature below cracking and above 100 C.

said noncracked residue and said rosin with a wet polyvalent metal oxide neutralizer and mixing themetai salts so formed with a filler, said metal salts and said filler being employed in a ratio of approximately 50 to 95 per cent by weight to the latter and 5 to 50 per cent by weight to the former.

9. -A method of preparing a material for roofing or flooring or insulating purposes or the like comprising mixing a noncracked pitchy residue obtained by vacuum steam distillation of tall oil with an organic substance containing resinous and fatty acids and with a resin, combining at a temperature below cracking and above 100 C. said pitchy residue and said organic substance with a wet metal oxide neutralizer of group II of the periodic system and mixing the metal salts so formed and said resin, acting as binder with a filleramounting to 50 to 95 per cent of Weight of the product.

10. A method as set forth in claim 9, wherein the metal salt of the pitchy residue amounts to at least 50 per cent by weight of the total amount of binder.

11. A method of preparing a metal for roofing or flooring or insulating purposes or the like comprising mixing a noncracked pitchy residue obtained by vacuum steam distillation of tall oil with an organic substance containing a resinous acid, combining at a temperature below cracking and above 100 C. a wet polyvalent metal oxide neutralizer, said neutralizer being employed in form of a water suspension, mixing the metal salts so formed with a filler selected from a group consisting of fibrous asbestos, powdered asbestos, rock wool, glass wool, fullers earth, powdered glass, silicon carbide, silicious earth and finely divided sand.

12. Composition of matter comprising a combination of a noncracked pitchy residue obtained by vacuum steam distillation of tall oil and a wet polyvalent metal oxide neutralizer and a filler containing fibrous and powdered substances, said metal salt and said filler being emplayed in a ratio tr approximately 50 to 95 per cent by weight of the latter and '5 to 50 per cent by weight of the former.

Number 13. A composition of matter consisting in a. combination of ingredients comprising about 1 part of a noncracked pitchy residue from the vacuum steam distillation of. tall oil having a melting point between 37 and 38 0., about 2 parts fibrous asbestos, about 2 parts finely ground asbestos, approximately about 0.1 part zinc oxide, about .6 part lithopon, about 0.25 part iron oxide red, and approximately 28 kgs. quartz sand, the ingredients being combined by weight and having a substantial portion of the water contained therein removed.

14. A composition of matter comprising a combination of about 1 part by weight of a noncracked pitchy residue from a vacuum steam distillation of tall oil having a melting point of 37 0., about 0L05 part by weight of rosin, approximately about 0.3 part by weight fibrous asbestos, about'0.05 part by weight cotton linters, approximately about 0.5 part by weight Spanish red, and about 0.06 part by weight umber and a precipitate resulting from a combination of about 0.4 part by weight aluminum sulphate dissolved in about 1 part by weight water, about 0.5 part by weight ground lime stone containing about 0.2 part by weight CaCOa, the mixture for substantially all water contained therein removed.

OTTO FRANS VALDEMAR FRICK.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date 1,051,769 Busehhaupt Jan. 28, 1913 2,090,577 Dillehay Aug. 17, 1937 2,178,770 Zaisser Nov. 7, 1939 2,306,352 Burrell Dec. 22, 1942 2,350,252 Sackett May 30, 1944 2,358,004 Dressler i Sept. 12, 1944 2,367,462 Farber Jan. 16, 1945 2,373,709 Rice Apr. 7, 1945 2,396,471 Osterhof Mar. 12, 1946 2,413,052 Kalman Dec. 24, 1946 2,448,621 Rice Sept. 7, 1948 2,481,356 Segessemann Sept. 6, 1949 

12. COMPOSITION OF MATTER COMPRISING A COMBINATION OF A NONCRACKED PITCHY RESIDUE OBTAINED BY VACUUM STEAM DISTILLATION OF TALL OIL AND A WET POLYVALENT METAL OXIDE NEUTRALIZER AND A FILLER CONTAINING FIBROUS AND POWDERED SUBSTANCES, SAID METAL SALT AND SAID FILLER BEING EMPLOYED IN A RATIO OF APPROXIMATELY 50 TO 95 PER CENT BY WEIGHT OF THE LATTER AND 5 TO 50 PER CENT BY WEIGHT OF THE FORMER. 